Process of making lakes



Patented Aug. 25, 1931 I L I I i UNITED STATES PATENT OFFICE.

NEMOURS 6: COMPANY, OF WILMINGTON, DELAWARE, ACORPORA'IION OE DELA- PROCESS OF MAKING LAKES No Drawing. t Application filed May 28, 1928. Serial No. 281,373.

This invention relates to .dye lakes, and is better and the character of the precipitate more particularlyto lakes 'producedby 0011- can be controlled With certainty. It may be version of the dye formedby coupling diazstated that the effect of the presence of the otized 2-amino-naphthalene-l-sulfonic acid beta-naphthol is to prevent the formation of With beta-naphtho-l into the barium and callargeplate-like crystals of the diazotized To- 59 cium salts. i V bias acid. The crystals remain very fine and In the process of making these barium and are in the form of needles instead of plates. calcium salts the 2-amino-naphthalene-l-sul- These needle-like crystals are the ones that fonic acid (Tobias acid) diazotizes slowly are needed fora rapid, uniform coupling.

: and gives rise to a relative insoluble diaz- Why the presence of the naphthol should con- 55 40 presence of finely divided beta-naphthol.

,onium compound. In order to, bring about trol the SIZE. of the crystals is not definitely the coupling, it is necessary'to heatthecomknown. v t pound almost to the boiling point on account The following examples are presented as of the poor solubility of the diazotized Tospecific embodiment of workingformulae of bias acid. In consequence, largecrystals are my invention, but it will be understood, of Qo 5 produced, and these large crystals resist concourse, that these are illustrative only, and version into barium and calcium salts beare not to be taken as a limitation thereof. cause of their small surface'a'nd insolubility. M k As a result, it has been found diflicult to pro- 6 mm mum 1 2o duce lakes in good yields, that is, lakes that Tub I z- 5 exhibit good strength when ground in 011, V .Percent as might be expected from the cause of the 300 grams beta-naphthoL 100 difficulty, and also it has been hard to C n r 10.0 grams caustic soda 100 the exact color of the roduct'which varies from a'yellow to a blu d shade" according to 3 1 h j lf 1n the t fl'm the size of the particles of pigment; SOC y eatmgto 140 d Q 7 An object of my invention, therefore, is I k y total m 500 G 1 ll s the productionof an improved diazonium 59111131011 32 h Add-cenough 1% compound. A further object of my invention o p i temperature C t hr gh t is the production of compounds of this kind the p ing. T0 the beta-naphthol 'solll i lb that exhibits good strength-when converted d t I c 1 1 7 Per cent 323 51322 9 2, 325 160 is iipperuqas 16 40.0 grams acetlc ac1d 99.5 Now, according to my invention the diffihydrochlorlc field culties heretofre experiencedare eliminated A the acetic acid then ft stirring by proceedmg m the manner mdlcatedhere" few minutes add the hydrochloric acid. Agiinafter. Instead of diazotizing the Tobias acid git? i i alone I carry out the diazotization 1n the i 4510 g ms mi p Ls fioib .86 Under these conditions if, after the diazotiza- 1c dlssolved}? d i tion is complete, the acidity is reduced to that grams calls/51G $0 a (10% so ut on 1n of bi-carbonate,-or the mixture made slight- W and 2 h ly alkaline coupling takes place v i.v I Make up volume to about 800 cc. After 45. formly and much more rapidly. The yield 'cooling with ice to 32 Redd:

' water) at 68 F. (100%). Follow immediately by 60.0 grams barium chloride (10% solution in water) at 68 F. as rapidly as possible. Agitate 10 minutes. Heat to 170 F. slowly. Dilute with water. Stir 4 hours. WVash twice, filter and dry at 130 F.

Light barium lake Tub I Per cent 30.0 grams beta-naphthol 100 10.0 grams caustic soda (10% solution. in water) 100 Dissolve the beta-naphthol in the caustic by heating to 140 F. Add:

400 cc. water making total volume of 500 cc. Cool this solution to 32 F. with .ice. Add: f i r 60.0 grams barium chloride 10% solution in water) to the bcta-naphthol under good agitation. Adjust temperature to 32 F. with ice. Stir for 10 minutes.

Tub II Dissolve 45.0 grams 2-a1nino-uaphthalene l-sulfonic acid (100%) in 8.8 grams caustic soda (10% solution in water) and 250 cc. water (hot). Make up to a volume of about 800 cc. After cooling with ice to 32 F. add:

13.8 grams sodium nitrite 100% (10% solution in water) to the cooled 2-amino-naphthalene-l-sulfonic acid solution. Add the 2-amino-naphthalene-l-sulfonic acid solution at 32 F. slowly to the betanaphthol suspension and stir 5 minutes, at a temperature of 32 F., and then add:

Per cent 40.0 grams acetic acid 99. 5 71.0 grams hydrochloric acid 37. 5

Stir for a few minutes.

Extra deep barium Zaice Tub I Per cent 30.0 grams beta-naphthol 100 10.0 grams caustic soda 100 Dissolve the beta-naphthol in the caustic soda and 100 cc. water by heating to 140 F. Dilute the beta-naphthol solution to a final volume of 500 cc. with cold water. Cool to 50 F. Add:

40.0 grams acetic acid (99.5

80.0 grams hydrochloric acid (37.36%)

Agitate slowly 3 minutes.

Tub II 45.0 grams 2-amino-naphthalene-l-sulfonic acid (99.8%)

8.8 grams caustic soda (100%) Dissolve the 2-amino-naphthalene-l-sulfonic acid in the caustic and 88 cc. water. Make up to a final volume of 300 cc. Cool to 50 F.

Combining I and II:

Add the 2-amino-naphthalene-l-sulfonic acid solution rapidly to the acid beta-naphthol suspension. Then add:

15.5 grams sodium nitrite (100%) in 155 cc. water (cold)50 F. Diazotize 2 minutes. Then add rapidly 43.0 grams caustic soda (100%) in 433 cc. water at 50 F. Immediately follow with:

60.0 grams barium chloride (100%) in 600 1 cc. water at 50 F. Heat slowly to 170 F.

in hour. During the heating, test at frequent intervals for alkali. There should be a slight test to brilliant yellow at all times during the coupling. If no test is obtained add more caustic until the desired test is acquired. Dilute with water. l/Vash three times, filter and dry at 140 F.

UaZcz'wm lake Tub I 30.0 grams beta-naphthol 100%.

10.0 grams caustic soda (10% solution in water) (100%) 70 F. Dissolve the betanaphthol in the caustic soda by heating to 140 F. Hold at this temperature until all the beta-naphthol is dissolved. Make up to 500 cc. with water at 100 F. Cool the solution to 32 F. with ice, then add:

40.0 grams acetic acid 99.5%. Follow immediately with 71.0 grams hydrochloric acid 37.36%. Stir 5 minutes.

Tub II 45.0 grams 2-amino-naphthalene-1-sulfonic acid 100% 8.8 grams caustic soda (10% solution in water) (100%) 70 F. Paste the 2-aminonaphthalene-l-sulfo-nic acid in the caustic soda. Then add 300 cc. water at 212 F. Immediately coolwith ice to 32 F. Final volume of ice and 2-amino-naphthalene-1-sulfonic acid solution should not exceed 800 cc.

Combining I and II Add the Q-amino-naphthalene-l-sulfomc' acid solution during a 5 minuteperiod to the acid beta-naphthol suspension at 32 F. Run in slowly during the course of 5 minutes, then add:

13.8 grams sodium nitrite (10% solution in water) F. Test for nitrite (should be distinctly positive test to potassium starch iodide). Diazotize 5 minutes while holding at a temperature of 32 F. After diazotization is complete add:

35.0 grams caustic soda (10% solution in water) at 70 F. in 1 minute. Follow the addition of caustic soda immediately with 35.0 grams calcium chloride (10% solution in water) at 70 F. during 1 minute. Heat slowly in 1 hour to 170 F. There should be a negative test at all times to brilliant yellow paper and a positive test to blue litmus. After heating is complete subject the coupling to A hours rapid agitation. Then dilute with water. Wash three times, filter and dry at F. F.

As many apparently widely different embodiments of this invention may be made without departing from the spirit thereof, it is to be understood that I do not intend to limit myself to the specific embodiments thereof except as indicated in the appended claims.

I claim:

1. In the process of producing intermediates for lakes, the step which comprises diazotizing 2-amino-naphthalene-l-sulfonic acid in the presence of beta-naphthol.

2. The process of producing alkaline earth metal lakes, which comprises 'diazotizing 2-amino-naphthalene-1-sulfonic acid in the presence of beta-naphthol and adding to the diazotized acid a solution containing a soluble alkaline earth metal salt.

3. The process of producing barium lakes, which comprises diazotizing 2-amino-naphthalene-l-sulfonic acid in the presence of beta-naphthol and adding to the diazotized acid a solution containing a soluble barium salt. a

4. The process of producing barium lakes, which comprises diazotizing 2-a1nino-naphthalene-l-sulfonic acid in the presence of beta-naphthol and adding to the diazotized acid a solution containing barium chloride.

In testimony whereof, I aflix my signature.

THOMAS A. MARTONE. 

